Bisphenol polyether oligomers, methods of manufacture, and polycarbonates made therefrom

ABSTRACT

A bisphenol polyether oligomer composition comprising greater than 90 wt. % of an oligomer of the formula 
     
       
         
         
             
             
         
       
     
     wherein R a , R b , and R c  are each independently a C 1-12  alkyl, C 1-12  alkoxy, or C 1-12  alkylarylene,
 
each X a  is independently a single bond, —O—, —S—, —S(O)—, —S(O) 2 —, —C(O)—, or a C 1-18  organic group,
 
G is H or
 
     
       
         
         
             
             
         
       
     
     p, q, and t are each independently integers of 0 to 4, n is 1 to 10; and wherein the bisphenol polyether oligomer composition comprises: a total halide content of less than 1000 ppm, less than 1000 ppm of —CH 2 OH groups, less than 5 wt. % cyclic oligomers, and less than 100 ppm of a bisphenol of the formula 
     
       
         
         
             
             
         
       
     
     wherein R a , R b , X a , p and q are the same as in the oligomer.

BACKGROUND

This disclosure relates to bisphenol polyether oligomers, polycarbonatesmade from the bisphenol polyether oligomers, methods for theirmanufacture, and uses thereof.

Polycarbonates are useful in a wide variety of applications at least inpart because of their good balance of properties, such as moldability,heat resistance and impact properties among others. Polycarbonates canbe manufactured through a transesterification reaction of an aromaticdihydroxy monomer and a carbonyl source under melt or interfacialpolymerization conditions.

While polycarbonates of different formulations and grades arecommercially available, there remains a need for polycarbonate withresidual monomer (if any) and with hydrolytic or thermolytic degradationproducts that exhibit certain beneficial characteristics.

SUMMARY

Disclosed herein is a bisphenol polyether oligomer compositioncomprising greater than 90 wt. % of an oligomer of the formula

wherein

R^(a), R^(b), and R^(c) are each independently a C₁₋₁₂ alkyl, C₁₋₁₂alkoxy, or C₁₋₁₂ alkylarylene,

each X^(a) is independently a single bond, —O—, —S—, —S(O)—, —S(O)₂—,—C(O)—, or a C₁₋₁₈ organic group,

G is H or

p, q, and t are each independently integers of 0 to 4,

n is 1 to 10; and

wherein the bisphenol polyether oligomer composition comprises:

a total halide content of less than 1000 ppm,

less than 1000 ppm of —CH₂OH groups,

less than 5 wt. % cyclic oligomers, and

less than 100 ppm of a bisphenol of the formula

wherein R^(a), R^(b), X^(a), p and q are the same as in the oligomer.

Also disclosed is a polyether polycarbonate comprising repeatingcarbonate unit of the formula

wherein

R^(a), R^(b), and R^(c) are each independently a C₁₋₁₈ alkyl, C₁₋₁₈alkoxy or alkylarylene,

each occurrence of X^(a) is independently single bond, —O—, —S—, —S(O)—,—S(O)₂—, —C(O)—, or a C₁₋₁₈ organic group,

p, q, and t are each independently integers of 0 to 4; and

n is 1 to 10.

A polyether polycarbonate composition comprising the polyetherpolycarbonate is also disclosed.

In yet another embodiment, an article comprises the above-describedpolyether polycarbonate composition.

In still another embodiment, a method of manufacture of an articlecomprises molding, extruding, or shaping the above-described polyetherpolycarbonate composition into an article.

The above described and other features are exemplified by the followingdrawings, detailed description, examples, and claims.

DETAILED DESCRIPTION

The present disclosure provides polycarbonates, which when exposed todegradation conditions, for example conditions for thermolysis orhydrolysis of the polycarbonates, produce hydrostable degradants thathave low or no binding affinities at estradiol sites. The polycarbonatesare derived from bisphenol polyether oligomer compositions, which inturn can be prepared from bisphenols and dihaloxylenes.

The bisphenol polyether oligomer compositions comprise greater than 90wt. % of oligomers of formula (1)

wherein R^(a), R^(b), and R^(c) are each independently a C₁₋₁₂ alkyl,C₁₋₁₂ alkoxy, or C₁₋₁₂ alkylarylene; and n is 1 to 10; and p, q, and tare each independently integers of 0 to 4. It will be understood thatwhen p, q, or t is less than 4, the valence of each carbon of the ringis filled by hydrogen. Further in formula (1), G is H or

Also in formula (1), X^(a) is a bridging group connecting the twohydroxy-substituted aromatic groups, where the bridging group and thehydroxy substituent of each C₆ arylene group are disposed ortho, meta,or para (specifically para) to each other on the C₆ arylene group. In anembodiment, the bridging group X^(a) is single bond, —O—, —S—, —S(O)—,—S(O)₂—, —C(O)—, or a C₁₋₁₈ organic group. The C₁₋₁₈ organic bridginggroup can be cyclic or acyclic, aromatic or non-aromatic, and canfurther comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur,silicon, or phosphorous. The C₁₋₁₈ organic group can be disposed suchthat the C₆ arylene groups connected thereto are each connected to acommon alkylidene carbon or to different carbons of the C₁₋₁₈ organicbridging group. In an embodiment, p and q is each 1, and R^(a) and R^(b)are each a C₁₋₃ alkyl group, specifically methyl, disposed meta to thehydroxy group on each arylene group.

In an embodiment, X^(a) is a substituted or unsubstituted C₃₋₁₈cycloalkylidene, a C₁₋₂₅ alkylidene of formula —C(R^(c))(R^(d))— whereinR^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl, C₁₋₁₂cycloalkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl, or a group of the formula —C(═R^(e))— wherein Re is adivalent C₁₋₁₂ hydrocarbon group. Groups of this type include methylene,cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, aswell as 2-[2.2.1]-bicycloheptylidene, cyclohexylidene, cyclopentylidene,cyclododecylidene, and adamantylidene.

In another embodiment, X^(a) is a C₁₋₁₈ alkylene, a C₃₋₁₈ cycloalkylene,a fused C₆₋₁₈ cycloalkylene, or a group of the formula —B¹-G′-B²—wherein B¹ and B² are the same or different C₁₋₆ alkylene and G′ is aC₃₋₁₂ cycloalkylidene or a C₆₋₁₆ arylene. For example, X^(a) can be asubstituted C₃₋₁₈ cycloalkylidene of formula (2)

wherein R^(r), R^(p), R^(q), and R^(t) are each independently hydrogen,halogen, oxygen, or C₁₋₁₂ hydrocarbon groups; Q is a direct bond, acarbon, or a divalent oxygen, sulfur, or —N(Z)— where Z is hydrogen,halogen, hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl; r is 0 to 2,t is 1 or 2, q is 0 or 1, and k is 0 to 3, with the proviso that atleast two of R^(r), R^(p), R^(q), and R^(t) taken together are a fusedcycloaliphatic, aromatic, or heteroaromatic ring. It will be understoodthat where the fused ring is aromatic, the ring as shown in formula (2)will have an unsaturated carbon-carbon linkage where the ring is fused.When k is one and (I) is 0, the ring as shown in formula (2) contains 4carbon atoms, when k is 2, the ring as shown in formula (2) contains 5carbon atoms, and when k is 3, and the ring contains 6 carbon atoms. Inan embodiment, two adjacent groups (e.g., R^(q) and R^(t) takentogether) form an aromatic group, and in another embodiment, R^(q) andR^(t) taken together form one aromatic group and R^(r) and R^(p) takentogether form a second aromatic group. When R^(q) and R^(t) takentogether form an aromatic group, R^(p) can be a double-bonded oxygenatom, i.e., a ketone.

In addition to greater than 90 wt. % of oligomers of formula (1), thebisphenol polyether oligomer compositions are characterized by having atotal halide (F, Cl, Br, and I) content of less than 1000 parts permillion by weight (ppm) based on the total parts by weight of thecomposition, including 0 to 999 ppm, 0 to 900 ppm, 1 to 800 ppm, 1 to700 ppm, or 5 to 500 ppm, each based on the total parts by weight of thecomposition.

The bisphenol polyether oligomer compositions are further characterizedby having less than 1000 ppm of —CH₂OH groups based on the total partsby weight of the composition, including 0 to 999 ppm, 0 to 900 ppm, 1 to800 ppm, 1 to 700 ppm, or 5 to 500 ppm, each based on the total parts byweight of the composition. Content of —CH₂OH groups can be determined,for example, by infrared spectroscopy, nuclear magnetic resonancespectroscopy, or titration.

The bisphenol polyether oligomer compositions are still furthercharacterized by having less than 5 wt. % cyclic oligomers based on thetotal weight of the composition, including 0 to 4.9 wt. %, 0 to 4.0 wt.%, 0.001 to 3.0 wt. %, each based on the total weight of thecomposition. Cyclic oligomers are of the formula

wherein n is 1 or greater, e.g., 1 to 4 and R^(a), R^(b), R^(c), X^(a),and p, q and t are as defined above.

The bisphenol polyether oligomer compositions are still furthercharacterized by having less than 100 ppm of a bisphenol of formula (3)

wherein R^(a), R^(b), X^(a), p and q are the same as in the oligomer offormula (1). In an embodiment, the bisphenol polyether oligomercompositions comprise 0 to less than 100 ppm of the bisphenol of formula(3) based on the total parts by weight of the oligomer composition, or 0to 90 ppm or 0 to 80 ppm, or 1 to 50 ppm, each based on the total partsby weight of the oligomer composition. The bisphenol of formula (3)corresponds to the bisphenol used to manufacture the polyetheroligomers, as explained in more detail below.

A specific bisphenol polyether oligomer composition comprises anoligomer of formula (1a)

wherein n is 1 to 10, G is H or

a total halide content of less than 1000 ppm, less than 1000 ppm of—CH₂OH groups, less than 5 wt. % cyclic oligomers, and less than 100 ppmof a bisphenol wherein the bisphenol is bisphenol A.

An example of a bisphenol polyether oligomer composition wherein X^(a)is a substituted C₃₋₁₈ cycloalkylidene comprises a bisphenol polyetherphthalimidine oligomer of formula (1b)

wherein R^(a), R^(b), R^(c), G, p, q, t, and n are the same as informula (1), R³ is each independently a C₁₋₆ alkyl, j is 0 to 4, and R⁴is hydrogen, C₁₋₆ alkyl, or a substituted or unsubstituted phenyl, forexample a phenyl substituted with up to five C₁₋₆ alkyls; a total halidecontent of less than 1000 ppm; less than 1000 ppm of —CH₂OH groups; lessthan 5 wt. % cyclic oligomers; and less than 100 ppm of a bisphenolwherein the bisphenol is of formula (3b)

wherein R^(a), R^(b), R³, R⁴, p, q, and j are the same as in formula(1b). In an embodiment, in formulas (1b) and (3b), R⁴ is hydrogen,phenyl optionally substituted with up to five 5 C₁₋₆ alkyls, or C₁₋₄alkyl. In an embodiment, R⁴ is hydrogen, methyl, or phenyl, specificallyphenyl; and p, q, j, and t are 0.

Other exemplary bisphenol polyether oligomer compositions comprisegreater than 90 wt. % of bisphenol polyether oligomers of formula (1c)

wherein n is 1 to 10, G is H or

a total halide content of less than 1000 ppm; less than 1000 ppm of—CH₂OH groups; less than 5 wt. % cyclic oligomers; and less than 100 ppmof a bisphenol wherein the bisphenol is of formula 3(c).

Still other exemplary bisphenol polyether oligomer compositions comprisegreater than 90 wt. % of bisphenol polyether oligomers of formula (1d)

wherein n is 1 to 10, G is H or

a total halide content of less than 1000 ppm; less than 1000 ppm of—CH₂OH groups; less than 5 wt. % cyclic oligomers; and less than 100 ppmof a bisphenol wherein the bisphenol is of formula 3(d).

As described in further detail below, the bisphenol polyether oligomersare derived by reaction of a bisphenol. Bisphenols can be specificallymentioned are 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one),1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC), and1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (isophoronebisphenol.

Other specific bisphenols that can be used to manufacture the bisphenolpolyether oligomers include, but are not limited to,4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantane, alpha,alpha′-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,9,9-bis(4-hydroxyphenyl)fluorene, 3,3-bis(4-hydroxyphenyl)phthalimide,or the like.

As in other embodiments, the bisphenol polyether compositionsmanufactured using any of the foregoing bisphenols comprise greater than90 wt. % of the bisphenol polyether oligomer having 1 to 10 repeatunits, wherein the endgroups G are H or

a total halide content of less than 1000 ppm; less than 1000 ppm of—CH₂OH groups; less than 5 wt. % cyclic oligomers; and less than 100 ppmof the bisphenol.

A combination of two or more different bisphenols can be present in theoligomers. In these embodiments, the total number of repeat polyetherunits is 1 to 10, where the number of individual units varies dependingon the concentration and reactivity of each bisphenol. As in otherembodiments, the bisphenol polyether compositions manufactured using acombination of two or more different bisphenols comprise greater than 90wt. % of the bisphenol polyether oligomer having 1 to 10 repeat units,wherein the endgroups G are H or

a total halide content of less than 1000 ppm; less than 1000 ppm of—CH₂OH groups; less than 5 wt. % cyclic oligomers; and less than 100 ppmof the bisphenols.

An example of a bisphenol polyether composition manufactured using acombination of two different bisphenols comprises greater than 90 wt. %of a bisphenol A-phthalimidine polyether oligomer of the formula

wherein R^(a), R^(b), and R^(c) are each independently a C₁₋₁₂ alkyl,C₁₋₁₂ alkoxy, or C₁₋₁₂ alkylarylene, R³ is each independently a C₁₋₆alkyl, R⁴ is hydrogen, C₁₋₆ alkyl, or a substituted or unsubstitutedphenyl, p, q, j, and t are each independently integers of 0 to 4, α is 1to 10 and β is 1 to 10, provided that α+β is 2 to 10, G is H or

and A is

andwherein the bisphenol is bisphenol A, a bisphenol of formula (3b),wherein R^(a), R^(b), R³, R⁴, p, q, and j are the same as defined forformula (3b), or a combination of bisphenol A and a bisphenol of formula(3b).

The bisphenol polyether oligomers can be prepared by reacting thebisphenol of formula (3)

with an aromatic dihalide of formula (4)

in the presence of an alkaline metal salt, for example, sodiumhydroxide, potassium hydroxide, or a combination thereof wherein R^(a),R^(b), R^(c), X^(a), p, q, and t are as defined in formula (1), and X isCl or Br.

Specific examples of aromatic dihalides of formula (4) includeα,α′-dibromo-p-xylene, α,α′-dichloro-p-xylene, di(chloromethyl)benzenes,and combinations comprising at least one of the foregoing.

The conditions for the synthesis can vary widely depending on thereactants. In general the synthesis is carried out with agitation in aninert solvent, for example, chlorobenzene, toluene, benzene, and thelike, specifically a polar aprotic solvent such as dimethyl sulfoxide,sulfolane, tetrahydrofuran, N-methyl pyrrolidinone, N,N-dimethylacetamide, and the like. The reaction can be conducted at atmospheric orhigher pressure, and at an elevated temperature, for example 30 to 180°C. In some embodiments the reaction is conducted with less than 100 ppmof water present.

The bisphenol polyether oligomers can have a weight average molecularweight of 300 to 5000 Daltons, specifically 500 to 2,000 Daltons, asmeasured by gel permeation chromatography (GPC), using a crosslinkedstyrene-divinylbenzene column and calibrated to polycarbonatereferences. GPC samples are prepared at a concentration of 1 mg per ml,and are eluted at a flow rate of 1.5 ml per minute.

In a particularly advantageous feature, the bisphenol polyetheroligomers are hydrolytically stable, particularly under conditions thatcan degrade polycarbonates as described in further detail below. Withoutwishing to be bound by theory, it is believed that the bisphenolpolyether oligomers show very low or no estradiol-like binding activitybecause they are highly insoluble in biological systems, and thereforedo not reach high concentrations in such systems; and because they aretoo large to fit into estradiol binding sites.

The lack of significant estradiol-like binding activity can becharacterized by a determination of their half maximal inhibitoryconcentration (IC₅₀) for alpha or beta in vitro estradiol receptors. Asused herein, the term half maximal inhibitory concentration (IC₅₀) is aquantitative measure that indicates how much of a particular substance,i.e., an inhibitor, is needed to inhibit a given biological process orcomponent of a process, by one half. In other words, it is the halfmaximal (50%) inhibitory concentration (IC) of a substance (50% IC, orIC₅₀). It is commonly known to one of ordinary skill in the art and usedas a measure of antagonist drug potency in pharmacological research. The(IC₅₀) of a particular substance can be determined using conventionalcompetition binding assays. In this type of assay, a singleconcentration of radioligand (such as an agonist) is used in every assaytube. The ligand is used at a low concentration, usually at or below itsK_(d) value. The level of specific binding of the radioligand is thendetermined in the presence of a range of concentrations of othercompeting non-radioactive compounds (usually antagonists), in order tomeasure the potency with which they compete for the binding of theradioligand. Competition curves may also be computer-fitted to alogistic function as described under direct fit. The IC₅₀ is theconcentration of competing ligand which displaces 50% of the specificbinding of the radioligand.

The bisphenol polyether compositions do not exhibit a half maximalinhibitory concentration (IC₅₀) less than 0.0025 M for alpha and/or betain vitro estradiol receptors. The upper range of the IC₅₀ is notparticularly limited, and in some embodiments cannot exceed thesolubility limit of the bisphenol polyether compositions in the aqueoustest solutions. In other embodiments, the bisphenol polyethercompositions do not exhibit a half maximal inhibitory concentration(IC₅₀) less than 0.00025 M or greater than 0.001 M, for alpha and/orbeta in vitro estradiol receptors.

The bisphenol polyether oligomer compositions can be used to preparepolycarbonates. “Polycarbonate” as used herein means a polymercomprising repeating structural carbonate units of formula (5)

wherein R^(a), R^(b), R^(c), p, q, t, and n are the same as defined informula (1). In an embodiment, the polycarbonate comprises 5 to 500 or 5to 200 repeating structural carbonate units of formula (5).

In specific embodiments, the polycarbonate comprises repeatingstructural carbonate units of formula (5a), formula (5b), formula (5c),formula (5d), or formula (5e)

wherein n is 1 to 10;

wherein n is 1 to 10;

wherein n is 1 to 10;

wherein R⁴ is phenyl or methyl and n is 1 to 10;

wherein α is 1 to 10 and β is i to 10, provided that α+β is 2 to 10, andA is

or a combination comprising at least one of the foregoing. Thepolycarbonate of formula (5e) is an example of a polycarbonate derivedfrom an oligomer manufactured from two or more different bisphenols,i.e., a polyether oligomer of formula (1e). Polycarbonates can also bemanufactured from two or more different polyether oligomers, for examplea combination of polyether oligomers of formulas (1a) and (1b), or acombination of polyether oligomers of formulas (1a) and (1e).

“Polycarbonates” thus includes homopolycarbonates (wherein eachcarbonate repeating unit is the same), copolymers comprising differentcarbonate repeating units (“copolycarbonates”), and copolymerscomprising carbonate units and other types of polymer units, such asester units or siloxane units.

Copolymers comprising different carbonate repeating units can comprisebisphenol polyether carbonate units and non-bisphenol polyethercarbonate units. Such units can be derived from the bisphenols offormula (3), 2,7-dihydroxypyrene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and2,7-dihydroxycarbazole; resorcinol, substituted resorcinol compoundssuch as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol,5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromoresorcinol, or the like, catechol, hydroquinone, and substitutedhydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone,2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone,2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like. In anembodiment, the thermolytic and hydrolytic degradation products of thepolycarbonates do not exhibit a half maximal inhibitory concentration(IC₅₀) less than 0.00025 M for alpha or beta in vitro estradiolreceptors. According to further embodiments, thermolytic and hydrolyticdegradation products derived from the non-bisphenol polyether units donot exhibit a half maximal inhibitory concentration (IC₅₀) less than0.0003 M, 0.00035 M, 0.0004 M, 0.00045 M, 0.0005 M, 0.00075 M, or even0.001 M, for alpha or beta in vitro estradiol receptors. The upper rangeof the IC₅₀ is not particularly limited, and in some embodiments cannotexceed the solubility limit of the thermolytic and hydrolyticdegradation products derived from the non-bisphenol polyether units inthe aqueous test solutions. In other embodiments, thermolytic andhydrolytic degradation products derived from the non-bisphenol polyethercarbonate units do not exhibit any identifiable half maximal inhibitoryconcentration (IC₅₀) less than 0.00025 M, or greater than 0.001 M, foralpha and/or beta in vitro estradiol receptors.

A specific type of copolymer is a poly(ester-carbonate), also known as apolyester-polycarbonate. Such copolymers further contain, in addition torecurring carbonate units of formula (7), repeating units of formula (6)

wherein J is a divalent group derived from a bisphenol polyetheroligomer of formula (1); and T is a divalent group derived from adicarboxylic acid (including a reactive derivative thereof), and can be,for example, a C₂₋₂₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀arylene. Copolyesters containing a combination of different T and/or Jgroups can be used. The polyester units can be branched or linear.

In an embodiment, J is derived from a bisphenol polyether oligomer offormula (1), for example, an oligomer of formula (1a).

Aromatic dicarboxylic acids that can be used to prepare the polyesterunits include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, or a combination comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids include terephthalic acid, isophthalic acid,naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or acombination comprising at least one of the foregoing acids. A specificdicarboxylic acid comprises a combination of isophthalic acid andterephthalic acid wherein the weight ratio of isophthalic acid toterephthalic acid is 91:9 to 2:98. In still other embodiments,thermolytic and hydrolytic degradation products derived frompolycarbonate compositions do not exhibit any identifiable half maximalinhibitory concentration (IC₅₀) less than 0.00025 M, 0.0003 M, 0.00035M, 0.0004 M, 0.00045 M, 0.0005 M, 0.00075 M, or even 0.001 M, for alphaand/or beta in vitro estradiol receptors. The upper range of the IC₅₀ isnot particularly limited, and in some embodiments cannot exceed thesolubility limit of the thermolytic and hydrolytic degradation productsderived from polycarbonate compositions in the aqueous test solutions.In other embodiments, thermolytic and hydrolytic degradation productsderived from polycarbonate compositions do not exhibit any identifiablehalf maximal inhibitory concentration (IC₅₀) less than 0.00025 M, orgreater than 0.001 M, for alpha and/or beta in vitro estradiolreceptors.

The molar ratio of ester units to carbonate units in the copolymers canvary broadly, for example 1:99 to 99:1, specifically 10:90 to 90:10,more specifically 25:75 to 75:25, or 2:98 to 15:85, depending on thedesired properties of the final composition.

Polycarbonates and poly(ester-carbonate)s can be manufactured byprocesses such as interfacial polymerization and melt polymerization.Although the reaction conditions for interfacial polymerization canvary, an exemplary process generally involves dissolving or dispersing abisphenol ether oligomer in aqueous caustic NaOH or KOH, adding theresulting mixture to a water-immiscible solvent, and contacting thereactants with a carbonate precursor in the presence of a catalyst suchas, for example, a tertiary amine or a phase transfer catalyst, undercontrolled pH conditions, e.g., 8 to 10.

The water-immiscible solvent can be, for example, methylene chloride,1,2-dichloroethane, chlorobenzene, toluene, and the like.

Exemplary carbonate precursors include a carbonyl halide such ascarbonyl bromide or carbonyl chloride (phosgene) a bishaloformate of adihydroxy compound (e.g., the bischloroformate of bisphenol A,hydroquinone ethylene glycol, neopentyl glycol, or the like), and diarylcarbonates. Combinations comprising at least one of the foregoing typesof carbonate precursors can also be used. The diaryl carbonate ester canbe diphenyl carbonate, or an activated diphenyl carbonate havingelectron-withdrawing substituents on the each aryl, such asbis(4-nitrophenyl)carbonate, bis(2-chlorophenyl)carbonate,bis(4-chlorophenyl)carbonate, bis(methyl salicyl)carbonate,bis(4-methylcarboxylphenyl) carbonate, bis(2-acetylphenyl) carboxylate,bis(4-acetylphenyl) carboxylate, or a combination comprising at leastone of the foregoing.

In the manufacture of poly(ester-carbonate)s by interfacialpolymerization, rather than using the dicarboxylic acid or dioldirectly, the reactive derivatives of the diacid or diol, such as thecorresponding acid halides, in particular the acid dichlorides and theacid dibromides can be used. Thus, for example instead of usingisophthalic acid, terephthalic acid, or a combination comprising atleast one of the foregoing acids, isophthaloyl dichloride, terephthaloyldichloride, or a combination comprising at least one of the foregoingdichlorides can be used.

Among tertiary amines that can be used as catalysts in interfacialpolymerization are aliphatic tertiary amines such as triethylamine andtributylamine, cycloaliphatic tertiary amines such asN,N-diethyl-cyclohexylamine, and aromatic tertiary amines such asN,N-dimethylaniline. Among the phase transfer catalysts that can be usedare catalysts of the formula (R³)₄Q⁺X, wherein each R³ is the same ordifferent, and is a C₁₋₁₀ alkyl; Q is a nitrogen or phosphorus atom; andX is a halogen atom or a C₁₋₈ alkoxy or C₆₋₁₈ aryloxy. Exemplary phasetransfer catalysts include (CH₃(CH₂)₃)₄NX, (CH₃(CH₂)₃)₄PX,(CH₃(CH₂)₅)₄NX, (CH₃(CH₂)₆)₄NX, (CH₃(CH₂)₄)₄NX, CH₃(CH₃(CH₂)₃)₃NX, andCH₃(CH₃(CH₂)₂)₃NX, wherein X is Cl⁻, Br⁻, a C₁₋₈ alkoxy or a C₆₋₁₈aryloxy. An effective amount of a phase transfer catalyst can be 0.1 to10 wt. %, or 0.5 to 2 wt. %, each based on the weight of dihydroxycompound in the phosgenation mixture.

An end-capping agent (also referred to as a chain stopper agent or chainterminating agent) can be included during polymerization to provide endgroups. The end-capping agents (and thus end groups) are selected basedon the desired properties of the polycarbonates. The end-capping agentlimits molecular weight growth rate, and thus controls molecular weightin the polycarbonate. Exemplary end-capping agents are exemplified bymonocyclic phenols such as phenol and C₁-C₂₂ alkyl-substituted phenolssuch as p-cumyl-phenol, resorcinol monobenzoate, and p- andtertiary-butyl phenol, monoethers of diphenols, such as p-methoxyphenol,and alkyl-substituted phenols with branched chain alkyl substituentshaving 8 to 9 carbon atoms, 4-substituted-2-hydroxybenzophenones andtheir derivatives, aryl salicylates, monoesters of diphenols such asresorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and theirderivatives, 2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives,mono-carboxylic acid chlorides such as benzoyl chloride, C₁-C₂₂alkyl-substituted benzoyl chloride, toluoyl chloride, bromobenzoylchloride, cinnamoyl chloride, and 4-nadimidobenzoyl chloride,polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydridechloride, and mono-chloroformates such as phenyl chloroformate,alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate,and toluene chloroformate. Combinations of different end groups can beused.

Preferred endcapping agents are selected such that any hydrolysisproduct of the selected chain stopper will not exhibit a half maximalinhibitory concentration (IC₅₀) less than 0.00025 M for alpha or beta invitro estradiol receptors. For example, and without limitation, asuitable chain stopper is phenol or phenyl monochloroformate. Thus, whenphenol is included as a chain stopper, the resulting polycarbonatecomprises phenol as an end cap to the polymer chain.

Branched polycarbonate blocks can be prepared by adding a branchingagent during polymerization. Preferred branching agents are selectedsuch that any hydrolysis product of the selected chain stopper will notexhibit a half maximal inhibitory concentration (IC₅₀) less than 0.00025M for alpha or beta in vitro estradiol receptors. These branching agentsinclude polyfunctional organic compounds containing at least threefunctional groups selected from hydroxyl, carboxyl, carboxylicanhydride, haloformyl, and mixtures of the foregoing functional groups.Specific examples include trimellitic acid, trimellitic anhydride,trimellitic trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol,tris-phenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene),tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha,alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride,trimesic acid, and benzophenone tetracarboxylic acid. The branchingagents can be added at a level of about 0.05 to about 2.0 wt. %.Combinations comprising linear polycarbonates and branchedpolycarbonates can be used.

The polycarbonates can have an intrinsic viscosity, as determined inchloroform at 25° C., of 0.3 to 1.5 deciliters per gram (dl/gm),specifically 0.45 to 1.0 dl/gm. The polycarbonates can have a weightaverage molecular weight of 10,000 to 100,000 Daltons, specifically10,000 to 80,000 Daltons, as measured by gel permeation chromatography(GPC), using a crosslinked styrene-divinylbenzene column and calibratedto polycarbonate references. GPC samples are prepared at a concentrationof 1 mg per ml, and are eluted at a flow rate of 1.5 ml per minute.

In some embodiments, the bisphenol polyether polycarbonates can have aglass transition temperature (Tg) of greater than 100° C., preferablygreater than 135° C., for example 135 to 210° C. Tg can be determined bydifferential scanning calorimetry (DSC) per ASTM D7426 with a 20° C./minheating rate.

In an important feature, each of the thermolytic and hydrolyticdegradation products of the polycarbonates does not exhibit a halfmaximal inhibitory concentration (IC₅₀) less than 0.00025 M for alpha orbeta in vitro estradiol receptors. According to further embodiments,thermolytic and hydrolytic degradation products derived frompolycarbonates do not exhibit a half maximal inhibitory concentration(IC₅₀) less than 0.0003 M, 0.00035 M, 0.0004 M, 0.00045 M, 0.0005 M,0.00075 M, or even 0.001 M, for alpha or beta in vitro estradiolreceptors. The upper range of the IC₅₀ is not particularly limited, andin some embodiments cannot exceed the solubility limit of thethermolytic and hydrolytic degradation products of the polycarbonates inthe aqueous test solutions. In other embodiments, thermolytic andhydrolytic degradation products derived from the polycarbonates do notexhibit any identifiable half maximal inhibitory concentration (IC₅₀)less than 0.00025 M, or greater than 0.001 M, for alpha and/or beta invitro estradiol receptors.

As used herein, “thermolytic and hydrolytic degradation product” is adegradation product arising from heat-, water-, or heat- andwater-mediated degradation of polycarbonates under conditions of normalmanufacture and especially use of the polycarbonates and articles madefrom the polycarbonates. Such conditions range from −40 to 150° C., from0 to 100% relative humidity. Tests to determine thermal and hydrolyticstability are known in the art, and can be used to generate thethermolytic and hydrolytic degradation products. Thermolytic andhydrolytic degradation products can be generated in many different ways:for example, exposure of polycarbonate parts to steam or hot water in anautoclave or oven testing for chemical decomposition products over time.The conditions of exposure to moisture can be varied to includedifferent pH as well as the presence of other additives such salts,soaps, water treatment chemicals, anti-scale additives, stabilizers,disinfectants and the like. Decomposition products may be determined inthe polycarbonate part or those decomposition products extracted intothe water. Analysis may be done by standard analytical techniques suchas liquid and gas chromatography, infra-red spectroscopy, or ultravioletspectroscopy. One such hydrolysis test is described in PolymerEngineering and Science, Vol. 22, April 1982, pp. 370-375. Anotherhydrolysis test protocol is described in is ASTM F1635-11. Hydrolysistesting of polymers varies widely with the end use needs of thepolycarbonate. Without being bound by theory, it is believed that underthermolytic and hydrolytic degradation conditions, polycarbonatesproduce the bisphenol polyether oligomers, which are themselvesthermolytically and hydrolytically stable. These oligomers are unlikelyto show biological activity as they are too insoluble in biologicalsystems to reach high problematic concentrations and too large to fitinto estradiol binding sites.

Polycarbonates manufactured as described herein are suitable for use ina wide variety of compositions and applications as is known in the art.Thus, an additive composition can be added to the purified polycarbonateto form a polycarbonate composition. The additive composition cancomprise one or more additives selected to achieve a desired property,with the proviso that the additive(s) are also selected so as to notsignificantly adversely affect a desired property of the polycarbonatecomposition. In particular, any thermolytic and hydrolytic degradationproducts derived from each of the additives in the polycarbonatecompositions do not exhibit a half maximal inhibitory concentration(IC₅₀) less than 0.00025 M, 0.0003 M, 0.00035 M, 0.0004 M, 0.00045 M,0.0005 M, 0.00075 M, or even 0.001 M, for alpha and/or beta in vitroestradiol receptors. The upper range of the IC₅₀ is not particularlylimited, and in some embodiments cannot exceed the solubility limit ofthe thermolytic and hydrolytic degradation products derived from each ofthe additives in the aqueous test solutions. In other embodiments,thermolytic and hydrolytic degradation products derived from each of theadditives do not exhibit any identifiable half maximal inhibitoryconcentration (IC₅₀) less than 0.00025 M, or greater than 0.001 M, foralpha and/or beta in vitro estradiol receptors. The additive compositionor individual additives can be mixed at a suitable time during themixing of the components for forming the composition. The additive canbe soluble and/or non-soluble in polycarbonate.

The additive composition can include an impact modifier, flow modifier,filler (e.g., a particulate polytetrafluoroethylene (PTFE), glass,carbon, mineral, or metal), reinforcing agent (e.g., glass fibers),antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) lightstabilizer, UV absorbing additive, plasticizer, lubricant, release agent(such as a mold release agent), antistatic agent, anti-fog agent,antimicrobial agent, colorant (e.g., a dye or pigment), surface effectadditive, radiation stabilizer, flame retardant, anti-drip agent (e.g.,a PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), or acombination comprising one or more of the foregoing. For example, acombination of a heat stabilizer, mold release agent, and ultravioletlight stabilizer can be used. In general, the additives are used in theamounts generally known to be effective. For example, the total amountof the additive composition (other than any impact modifier, filler, orreinforcing agent) can be 0.001 to 10.0 wt. %, or 0.01 to 5 wt. %, eachbased on the total weight of the polymer in the composition.

Suitable impact modifiers include natural rubber, fluoroelastomers,ethylene-propylene rubber (EPR), ethylene-butene rubber,ethylene-propylene-diene monomer rubber (EPDM), acrylate rubbers,hydrogenated nitrile rubber (HNBR) silicone elastomers, andelastomer-modified graft copolymers such as styrene-butadiene-styrene(SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butylene-styrene(SEBS), acrylonitrile-butadiene-styrene (ABS),acrylonitrile-ethylene-propylene-diene-styrene (AES),styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene(MBS), high rubber graft (HRG), and the like.

Any one or more of the additives, for example heat stabilizers or flameretardants, can be provided as a phosphorous-containing compound.Exemplary phosphorous containing compounds including phosphites,phosphonates, phosphates, or a combination thereof. Examples ofphosphite additives include diphenyl (C₁₋₁₈)alkyl phosphites, phenyldi(C₁₋₁₈)alkyl phosphites, tri(C₁₋₁₈)alkyl phosphites, triphenylphosphites, diphenyl pentaerythritol diphosphite, or any combinationthereof, wherein the phenyl groups can be substituted or unsubstituted,for example tris-(2,6-dimethylphenyl)phosphite, and tris-(mixed mono-and di-nonylphenyl)phosphite. In various embodiments, a phosphite orphosphonate or mixture thereof the additive can be present in an amountof, for example, from about 0.00001 wt. % to about 0.3 wt. %, or fromabout 0.0001 wt. % to about 0.01 wt. %. In other embodiments, aphosphite additive can have a molecular weight (Mw) of greater thanabout 200 Daltons.

Examples of phosphate additives include triphenyl phosphate, resorcinolphenyl diphosphate, spirobiindane phenyl diphosphate, di-tert-butylhydroquinone phenyl diphosphate, biphenol phenyl diphosphate, bisphenolA bis(diphenyl phosphate), hydroquinone phenyl diphosphate, or anycombination thereof. In various embodiments, the phosphates can beuseful in flame retardant polycarbonate blends, such as, for example,PC-ABS, PC-MBS, or PC-ABS-MBS blends. In an embodiment, an arylphosphate can be used at, for example, 1 to 30 wt. % of the composition,or 5 to 20 wt. % of the composition. In yet other embodiments, the arylphosphate will have a molecular weight of about 300 Daltons to about1500 Daltons. It should also be understood that, in view of thisdisclosure, any other suitable phosphorous-containing additive, orthermolysis or hydrolysis degradation product thereof, exhibiting a lackof estradiol binding activity characterized by the half maximalinhibitory concentration values described above can used.

The polycarbonate compositions can comprise a colorant, for exampleSolvent Green 3, Solvent Green 28, Solvent Green 38, Pigment Green 50,Pigment Green 36, Solvent Red 52, Solvent Red 101, Solvent Red 111,Solvent Red 135, Solvent Red 169, Solvent Red 179, Solvent Red 207,Pigment Red 101, Disperse Red 22, Vat Red 41, Solvent Orange 60, SolventOrange 63, Disperse Orange 47, Solvent Violet 13, Solvent Violet 14,Solvent Violet 36, Solvent Violet 50, Disperse Violet 26/31, PigmentBlue 29, Pigment Blue 60, Copper Phthalocyanine Pigment Blue 15.4,Disperse Blue 73, Solvent Blue 97, Solvent Blue 101, Solvent Blue 104,Solvent Blue 122, Solvent Blue 138, Pigment Yellow 53, Pigment Yellow138, Pigment Yellow 139, Disperse Yellow 201, Solvent Yellow 33, SolventYellow 114, Solvent Yellow 93, Solvent Yellow 98, Solvent Yellow 163,Solvent Yellow 160:1, Solvent Yellow 188, Pigment Brown 24, Amino KetoneBlack, chrome oxides, carbon black, channel black, Pigment Black 6,titanium dioxide, and a combination comprising at least one of theforegoing.

The polyether polycarbonate compositions can further comprise anadditional polymer that is a non-polyether polycarbonate, in a weightratio of polyether polycarbonate: additional polymer of 1:99 to 99:1, or10:90 to 90:10 or 20:80 to 80:20, for example. The additional or second(or more) polymer can comprise a polycarbonate, polyester, polyolefin,polyetherimide, styrene-acrylonitrile, acrylonitrile-butadiene-styrene,methyl methacrylate, methyl methacrylate-butadiene-styrene,styrene-maleic anhydride, styrene-butadiene-styrene,styrene-ethylene-butylene-styrene, polystyrene, or a combinationcomprising at least one of the foregoing. Preferably, thermolytic andhydrolytic degradation products derived from the additional polymer donot exhibit a half maximal inhibitory concentration (IC₅₀) less than0.00025 M for alpha or beta in vitro estradiol receptors. According tofurther embodiments, thermolytic and hydrolytic degradation productsderived from the additional polymer do not exhibit a half maximalinhibitory concentration (IC₅₀) less than 0.0003 M, 0.00035 M, 0.0004 M,0.00045 M, 0.0005 M, 0.00075 M, or even 0.001 M, for alpha or beta invitro estradiol receptors.

The polycarbonate compositions can be manufactured by various methodsknown in the art. For example, powdered polycarbonate, and otheroptional components are first blended, optionally with any fillers, in ahigh speed mixer or by hand mixing. The blend is then fed into thethroat of a twin-screw extruder via a hopper. Alternatively, at leastone of the components can be incorporated into the composition byfeeding it directly into the extruder at the throat and/or downstreamthrough a sidestuffer, or by being compounded into a masterbatch with adesired polymer and fed into the extruder. The extruder is generallyoperated at a temperature higher than that necessary to cause thecomposition to flow. The extrudate can be immediately quenched in awater bath and pelletized. The pellets so prepared can be one-fourthinch long or less as desired. Such pellets can be used for subsequentmolding, shaping, or forming

Shaped, formed, or molded articles comprising the polycarbonatecompositions are also provided. The polycarbonate compositions can bemolded into useful shaped articles by a variety of methods, such asinjection molding, extrusion, rotational molding, blow molding, andthermoforming. Some example of articles include computer and businessmachine housings such as housings for monitors, handheld electronicdevice housings such as housings for cell phones, electrical connectors,and components of lighting fixtures, ornaments, home appliances, roofs,greenhouses, sun rooms, swimming pool enclosures, and the like. Inaddition, the polycarbonate compositions are especially useful for foodcontact and medical applications. Food contact applications includearticles such as containers, especially re-usable containers, and aresubject to cleaning or autoclaving, and medical applications where thearticles are subject to cleaning or autoclaving.

Thermolytic and hydrolytic degradation products derived from thepolycarbonate compositions or articles comprising the polycarbonatecompositions do not exhibit a half maximal inhibitory concentration(IC₅₀) less than 0.00025 M for alpha or beta in vitro estradiolreceptors. According to further embodiments, thermolytic and hydrolyticdegradation products derived from polycarbonate compositions or articlesdo not exhibit a half maximal inhibitory concentration (IC₅₀) less than0.0003 M, 0.00035 M, 0.0004 M, 0.00045 M, 0.0005 M, 0.00075 M, or even0.001 M, for alpha or beta in vitro estradiol receptors. The upper rangeof the IC₅₀ is not particularly limited, and in some embodiments cannotexceed the solubility limit of thermolytic and hydrolytic degradationproducts derived from polycarbonate compositions or articles in theaqueous test solutions. In other embodiments, thermolytic and hydrolyticdegradation products derived from polycarbonate compositions or articlesdo not exhibit any identifiable half maximal inhibitory concentration(IC₅₀) less than 0.00025 M, or greater than 0.001 M, for alpha and/orbeta in vitro estradiol receptors.

The bisphenol polyether oligomers, polycarbonates, and polycarbonatecompositions are further illustrated by the following non-limitingexamples.

Examples Example 1 Synthesis of BPA Polyether Oligomer fromα,α′-Dibromo-p-Xylene

Bisphenol A (BPA) (17 grams), dibromo-p-xylene (10 grams), dimethylsulfoxide (DMSO, 40 ml), tetrahydrofuran (THF, 20 ml), and KOH (60 mL,50 aq.%) were charged into a three-neck flask equipped with a mechanicalstirrer and a thermocouple. The reaction mixture was heated at 60° C.for 16 hours. A small sample was taken from the reaction, neutralizedwith acetic acid and an ultra-high performance liquid chromatography(“UPLC”) spectrum showed the peaks for BPA, BPA ether dimer (n=1), andBPA ether trimer (n=2). After cooling, 30 ml of acetic acid was added tothe flask to adjust the pH to 6. The crude reaction mixture was mixedwith methanol, stirred for approximately 1 hour, and then filtered using#4 filter paper in a Buchner funnel. UPLC was run on the filteredsolids. There was a marked decrease of BPA (n=0) peak compared to theprevious small sample from the reaction mixture. The acidification withacetic acid and addition of methanol allowed the removal of >95% of theunreacted BPA giving purified phenolic capped polyether oligomers.Solids were further washed with methanol, and then stirred in methanolovernight. UPLC of the filtered solids showed only 0.99 area % of BPApeak. Further methanol treatment followed by filtration gave additionalreduction of free BPA, in some instances to less than 100 ppm. UPLCshowed no indication (less than 1%) of cyclic oligomers.

GPC (methylene chloride solution) showed normal distribution for thepolyether oligomers with weight average molecular weight (“Mw”) of 998g/mol and number average molecular weight (“Mn”) of 636 g/mol usingpolycarbonate standards. Trimer peak was the largest peak. The solidswere dried in an oven overnight at 60° C. Proton NMR was run and showedboth xylene methylene protons and BPA methyl group signals in theexpected ratio of about 4:3. Bromomethylene (phenyl-CH₂—Br) signals andaliphatic hydroxymethylene (phenyl-CH₂—OH) signal from potentialhydrolysis of the bromoxylene functionality were not detected (less than1000 ppm). The methanol-washed polyether oligomers had high level ofphenolic end groups (>95%) with less than 100 ppm BPA.

Example 2 Synthesis of BPA Polyether Oligomer fromα,α′-Dichloro-p-Xylene

BPA (21 grams), dichloro-p-xylene (7 grams), DMSO (60 ml), THF (30 ml),and KOH (62 grams, 50 aq.%) were charged into a three-neck flaskequipped with a mechanical stirrer and a thermocouple. The reactionmixture was heated at 60° C. for approximately 16 hours then cooled toroom temperature. Acetic acid (40 ml) was added to neutralize the crudeproduct to a pH of 6. UPLC was run on a small sample showing peaks forBPA, BPA ether dimer, and BPA ether trimer. Methanol was added. Themixture was stirred for approximately 1 hour then filtered using #4filter paper. UPLC was run on the filtered solids which showed a markeddecreased of BPA (n=0) peak as compared to the small reaction mixturesample. After three methanol washes, solids had less than 1% of BPA onUPLC. GPC of the polyether oligomers showed normal distribution curveand Mw of 1167 and Mn of 713 using polycarbonate standards. The dimerpeak appeared to be larger than the trimer peak on UPLC. It was notedthat when the solids were further washed with water, the pink color wasremoved and a white powder was obtained.

Example 3 Purification of Polyether Oligomers

As described above, washing the polyether oligomers with methanol atroom temperature (23° C.) was effective in removing BPA (n=0). BPAextraction and removal was more effective with a finely divided powderproviding more surface area and solvent access. When hot methanol wasused (>50° C.) not only was BPA removed but the n=1 dimer also dissolvedinto solution. The higher Mw polyether oligomer fraction n>2 was stillinsoluble. When the methanol oligomer mixture was filtered hot (>50° C.)the solid oligomers were isolated with no detectable BPA and nodetectable n=1 dimer. When the hot methanol solution was cooled the n=1dimer (BPA-X-1) precipitated from solution while the BPA remaineddissolved. Thus it was possible to remove BPA, isolate a pure n=1(dimer) portion and a higher n>2 oligomer content. The purified n=1dimer and the higher oligomers were analyzed for estrogenic activity asdescribed below.

BPA-X-1=BPA Xylene dimer (n=1) is4,4′-[1,4-Phenylenebis(methyleneoxy-4,1-phenylene(1-methylethylidene))]bisphenolFW=558 g/mol (GPC).

BPA-X-3.5=BPA Xylene oligomer (n=3.5) is1,4-Bis(chloromethyl)benzene-bisphenol A copolymer FW=1345 g/mol (GPC).

Example 4 Evaluation of Phenolic Compounds and Polyether Oligomers

Estradiol Binding: Utilizing a conventional in vitro competitive bindingassay, estradiol binding activity was quantified by the half maximalinhibitory concentration (IC₅₀) value, which was evaluated for variousphenolic compounds capable for use as component starting materials inthe manufacture of polyether carbonate compositions.

Polyether oligomers and other phenolic materials mimic or replicatevarious chemical species that could be produced under some conditions,for example high (pH=8 to 12) or low (pH=1 to 6) pH, as hydrolysisdegradation products derived from polycarbonates comprising thecomponent starting materials. Specifically, (IC₅₀) bindingconcentrations for both the alpha or beta in vitro estradiol receptorsfor various compounds in Table 1 were tested. A set of tests were runusing a standard competitive estradiol binding assay. Samples weredissolved in DMSO. The various phenolic compounds were then tested at upto seven different concentrations for each test phenolic compound. Eachof those tests was run in triplicate. Tests were conducted bydisplacement of a radio-ligand. A 17b-estradiol control sample was runto ensure proper binding of the natural hormone under the testconditions.

The phenolic compounds or polyether oligomers (Table 1) wereinvestigated as to their binding affinity for recombinant humanestradiol receptors (rhER) alpha (α) and beta 1 (β1) in vitro.17β-Estradiol (E₂) was used as a standard whose relative bindingaffinity was defined as 100%. Competitive binding assays were performedby incubating rhER alpha (a) and beta 1 (β1) with 10 nM [³H]estradiol(the radio ligand) in the presence or absence of increasingconcentrations, 0.25 to 250,000 nM, of the test compounds of Table 1 (nMis nano molar). Each data point is the average of at least two assays.Stock solutions of the compounds of Table 1 were prepared at 10×E-2 M in100% DMSO (dimethyl sulfoxide). The BPA xylene dimer (BPA-X-1) and BPAxylene oligomers (BPA-X-3.5) as described in Example 2 were comparedwith BPA, p-cumyl phenol, phenol and an estradiol control. The compoundswere diluted 10 fold in binding buffer and then 1:4 in the final assaymix. The final concentration of DMSO in the assay well was 5%. In someinstances the highest concentration of the test compound was 2.5×E-4 M(250,000 nM). In some instances the compounds of Table 1 were tested atseven concentrations over log increments. The lowest concentration was2.5×E-10 M (0.25 nM). The IC50 is the concentration of test substance atwhich about 50% of the radio labeled estradiol was displaced from theestradiol receptor.

Binding assays were run under standard conditions as follows: purifiedrecombinant human (rh) ERα and rhERβ were incubated with 10 nM³H-estradiol in 10 mM Tris, pH 7.5, 10% glycerol, 1 mg/ml ovalbumin and2 mM dithiothreitol (DTT) to measure total binding. The phenolic testcompounds were added at several concentrations. Samples were incubatedat 4° C. overnight. ³H-E2-ER complexes were separated from unboundradioligand by addition of 50% aq. hydroxy apatite, filtration, andwashing. All incubations were run in triplicate. Samples were analyzedusing a LKB Wallac Rackbeta model 1209 liquid scintillation counter.

Surprisingly under conditions where the parent compound (BPA) was seento bind to both receptors (see Table 1), the phenolic oligomers derivedfrom BPA, i.e., BPA xylene dimer (n=1), and BPA xylene oligomer (n˜3.5)gave no detectable binding, even at the highest concentration. That is,no binding can be measured using standard biochemical analysistechniques to test estradiol binding activity. Even at a concentrationof 2.5×E-4 M there was no displacement of estradiol. Higherconcentrations, larger values of IC50, indicate less binding affinity(the test compound is less estradiol like in cell binding).

The BPA xylene oligomer (n=3.5) did not completely dissolve at allconcentrations. At the concentrations tested it showed no binding. Thelow solubility of the polyether oligomers is yet a further indicationthat it is unavailable under normal biological conditions to take partin any binding to any endocrine receptor.

TABLE 1 Estradiol Competition Example Compounds IC₅₀ rhER alpha IC₅₀rhER beta Control A 17b-estradiol control (CAS#5028-2)   1.0 × E−9   8.2× E−9 Control B Bisphenol A   2.0 × E−4   4.5 × E−6 Control C p-CumylPhenol   1.4 × E−4   9.8 × E−6 BPA-X-1 BPA-Xylene dimer n = 1 >2.5 ×E−4 >2.5 × E−4 BPA-X-3.5 BPA-Xylene oligomers n = 3.5 >2.5 × E−4 >2.5 ×E−4 Phenol Phenol (polycarbonate end cap) >2.5 × E−4 >2.5 × E−4 NotesIC₅₀ is the concentration of the candidate that >2.5 × 10⁴ compounds didnot compete to displaces 50% of the radioactive ligand from the extentof 50% with radiolabeled 17B- the rhER cells estradiol at the highestconc. (250,000 nM) tested; no IC50 can be determined

It was also noted that estradiol binds at very low concentrations of 1.0to 8.2×E-9 M in control experiment A and is much more active, by over 4orders of magnitude, than any of the compounds tested including BPA(example B). In these tests BPA and p-cumyl phenol (example C) have avery low level of binding, the polyether oligomers have a non-detectablelevel of binding.

Example 5 Synthesis of Polycarbonate from BPA Polyether Oligomer

Methylene chloride (500 ml), water (300 ml), BPA-xylene methanol washedpolyether oligomer from Example 1 (9 grams), and triethylamine (“TEA”)(0.1 ml) were charged into a 2 L flask equipped with mechanical stirrer,chilled ethylene glycol condenser, pH probe, and caustic (NaOH)scrubbers for vent gas. The mixture was stirred for approximately 10minutes to allow the larger clumps of oligomer to disperse prior tophosgenation. Phosgene was added for 10 min at 1 g/ruin rate while 30wt. % aqueous NaOH was added as necessary to maintain a pH of 9. Areaction sample of the polyether carbonate had an Mw of about 24,000determined by GPC using polycarbonate standards. This showed that thelower molecular weight polyether oligomers were capable of building to ahigh Mw polycarbonate indicating a high level of reactive diphenolic endcaps of the polyether oligomer.

The crude product was allowed to separate into two phases. The organicphase was separated, washed with 1N HCl, then three times with water.Hot water precipitation was used to isolate the polymer from solution;dropwise addition of the methylene chloride solution of the polymer toboiling water caused the methylene chloride solvent to flash from themixture leaving a polymer powder suspended in water. The polyethercarbonate powder was filtered from the water and dried in an ovenovernight at 60° C. The dried polymer powder had a Tg of 105° C. asdetermined by DSC as per ASTM D7426 with a 20° C./min heating rate. Tgwas measured on second heat. The polyether polycarbonate containingpolymer could be melt processed into a clear flexible film. In someinstances the polyether carbonate has a chloride content of less than 20ppm, a phenolic end group content of less than 20 meq/Kg polymer, atransition metal content of less than 20 ppm, and a residual phenolicmonomer content of less than 100 ppm.

Example 6 Synthesis of Mixed BPA N-Phenyl Phenolphthalein BisphenolPolyether Oligomer from α,α′-Dichloro-p-Xylene

BPA (70 grams), dichloro-p-xylene (35 grams), and 42 g N-phenylphenolphthalein-p,p-bisphenol (P3BP), DMSO (300 ml), THF (150 ml), andKOH (300 grams, 50 aq.% solution) were charged into a three-neck flaskequipped with a mechanical stirrer and a thermocouple. The reactionmixture was heated at 60° C. for approximately 16 hours then cooled downto room temperature. Acetic acid (40 ml) was added to neutralize thecrude product to a pH of 6. UPLC was run on a small sample showing peaksfor BPA, P3BP, BPA-P3BP dimer, and higher oligomers. Water and methanolwere added. The mixture was stirred for approximately 1 hour thenfiltered using #4 filter paper. The filtrate was further washed withmethanol. The solid was then suspended in methanol at room temp andstirred for several hours. After three methanol washes, the oligomershad less than 1% of BPA by UPLC analysis. GPC of the yellow polyetheroligomers showed normal distribution curve and Mw of 1215 Daltons and Mnof 687 Daltons using polycarbonate standards. The dimer peak appeared tobe larger than the trimer peak on UPLC. ¹HNMR analysis showed thepolyether oligomer to be ˜35% P3BP. No peaks related to cyclic oligomerwere observed. Chloro methylene (phenyl-CH₂—Cl) signals and aliphatichydroxyl methylene (Phenyl-CH₂—OH) signal from potential hydrolysis ofthe chloro xylene functionality, were not detected (less than 1000 ppm).The methanol washed polyether oligomers had high level of phenolic endgroups (>95%) with less than 100 ppm BPA.

Example 7 Synthesis of Polycarbonate from BPA-N-Phenyl PhenolphthaleinBisphenol (P3BP) Polyether Oligomer

Methylene chloride (500 ml), water (300 ml), BPA-P3BP methanol washedpolyether oligomer from Example 6 (9 grams), and triethylamine (“TEA”)(0.1 ml) were charged into a 2 L flask equipped with mechanical stirrer,chilled ethylene glycol condenser, pH probe, and caustic (NaOH)scrubbers for vent gas. The mixture was stirred for approximately 10minutes to allow the larger clumps of oligomer to disperse prior tophosgenation. Phosgene was added for 10 min at 1 g/ruin rate while 30wt. % aqueous NaOH was added as necessary to maintain a pH of 9. Areaction sample from the mixture had a Mw of about 32,000, Mn about13,000 as determined by GPC using polycarbonate standards. This showedthat the lower molecular weight polyether BPA-P3BP oligomers werecapable of building to a high Mw polycarbonate indicating a high levelof reactive diphenolic end caps of the polyether oligomer.

The crude product was allowed to separate into two phases. The organicphase was separated, washed with 1N HCl, then three times with water.Hot water precipitation was used to isolate the polymer from solution;dropwise addition of the methylene chloride solution of the polymer toboiling water, caused the methylene chloride solvent to flash from themixture leaving a polymer powder suspended in water. The polymer powderwas filtered from the water and dried in an oven overnight at 60° C. Thedried polymer powder had a Tg of 143° C. as determined by DSC as perASTM D7426 with a 20° C./min heating rate. Tg was measured on secondheat. The polyether polycarbonate polymer, which had a higher heatcapability than its BPA parent (Example 5) could be melt processed intoa clear flexible film.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. “Or” means “and/or.” Themodifier “about” used in connection with a quantity is inclusive of thestated value and has the meaning dictated by the context (e.g., includesthe degree of error associated with measurement of the particularquantity). The endpoints of all ranges directed to the same component orproperty are inclusive and independently combinable (e.g., ranges of“less than or equal to 25 wt. %, or 5 wt. % to 20 wt. %,” is inclusiveof the endpoints and all intermediate values of the ranges of “5 wt. %to 25 wt. %,” etc.). The suffix “(s)” is intended to include both thesingular and the plural of the term that it modifies, thereby includingat least one of that term (e.g., the colorant(s) includes at least onecolorants). “Optional” or “optionally” means that the subsequentlydescribed event or circumstance can or cannot occur, and that thedescription includes instances where the event occurs and instanceswhere it does not.

As used herein, a “combination” is inclusive of blends, mixtures,alloys, reaction products, and the like. Compounds are described usingstandard nomenclature. For example, any position not substituted by anyindicated group is understood to have its valency filled by a bond asindicated, or a hydrogen atom. A dash (“-”) that is not between twoletters or symbols is used to indicate a point of attachment for asubstituent. For example, —CHO is attached through carbon of thecarbonyl group.

As used herein, the term “hydrocarbyl” and “hydrocarbon” refers broadlyto a substituent comprising carbon and hydrogen, optionally with 1 to 3heteroatoms, for example, oxygen, nitrogen, halogen, silicon, sulfur, ora combination thereof; “alkyl” refers to a straight or branched chain,saturated monovalent hydrocarbon group; “alkylene” refers to a straightor branched chain, saturated, divalent hydrocarbon group; “alkylidene”refers to a straight or branched chain, saturated divalent hydrocarbongroup, with both valences on a single common carbon atom; “alkenyl”refers to a straight or branched chain monovalent hydrocarbon grouphaving at least two carbons joined by a carbon-carbon double bond;“cycloalkyl” refers to a non-aromatic monovalent monocyclic ormulticylic hydrocarbon group having at least three carbon atoms,“cycloalkenyl” refers to a non-aromatic cyclic divalent hydrocarbongroup having at least three carbon atoms, with at least one degree ofunsaturation; “aryl” refers to an aromatic monovalent group containingonly carbon in the aromatic ring or rings; “arylene” refers to anaromatic divalent group containing only carbon in the aromatic ring orrings; “alkylarylene” refers to an arylene group that has beensubstituted with an alkyl group as defined above, with 4-methylphenylenebeing an exemplary alkylarylene group; “arylalkylene” refers to analkylene group that has been substituted with an aryl group as definedabove, with benzyl being an exemplary arylalkylene group; “acyl” refersto an alkyl group as defined above with the indicated number of carbonatoms attached through a carbonyl carbon bridge (—C(═O)—); “alkoxy”refers to an alkyl group as defined above with the indicated number ofcarbon atoms attached through an oxygen bridge (—O—); and “aryloxy”refers to an aryl group as defined above with the indicated number ofcarbon atoms attached through an oxygen bridge (—O—).

Unless otherwise indicated, each of the foregoing groups can beunsubstituted or substituted, provided that the substitution does notsignificantly adversely affect synthesis, stability, or use of thecompound. The term “substituted” as used herein means that at least onehydrogen on the designated atom or group is replaced with another group,provided that the designated atom's normal valence is not exceeded. Whenthe substituent is oxo (i.e., ═O), then two hydrogens on the atom arereplaced. Combinations of substituents and/or variables are permissibleprovided that the substitutions do not significantly adversely affectsynthesis or use of the compound. Exemplary groups that can be presenton a “substituted” position include, but are not limited to, cyano;hydroxyl; nitro; azido; alkanoyl (such as a C₂₋₆ alkanoyl group such asacyl); carboxamido; C₁₋₆ or C₁₋₃ alkyl, cycloalkyl, alkenyl, and alkynyl(including groups having at least one unsaturated linkages and from 2 to8, or 2 to 6 carbon atoms); C₁₋₆ or C₁₋₃ alkoxys; C₆₋₁₉ aryloxy such asphenoxy; C₁₋₆ alkylthio; C₁₋₆ or C₁₋₃ alkylsulfinyl; C₁₋₆ or C₁₋₃alkylsulfonyl; aminodi(C₁₋₆ or C₁₋₃)alkyl; C₆₋₁₂ aryl having at leastone aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like, eachring either substituted or unsubstituted aromatic); C₇₋₁₉ alkylenearylhaving 1 to 3 separate or fused rings and from 6 to 18 ring carbonatoms, with benzyl being an exemplary arylalkyl; or arylalkoxy having 1to 3 separate or fused rings and from 6 to 18 ring carbon atoms, withbenzyloxy being an exemplary arylalkoxy.

All cited patents, patent applications, and other references areincorporated herein by reference in their entirety. However, if a termin the present application contradicts or conflicts with a term in theincorporated reference, the term from the present application takesprecedence over the conflicting term from the incorporated reference.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

What is claimed is:
 1. A bisphenol polyether oligomer compositioncomprising greater than 90 wt. % of an oligomer of the formula

wherein R^(a), R^(b), and R^(c) are each independently a C₁₋₁₂ alkyl,C₁₋₁₂ alkoxy, or C₁₋₁₂ alkylarylene, each X^(a) is independently asingle bond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organicgroup, G is H or

p, q, and t are each independently integers of 0 to 4, n is 1 to 10; andwherein the bisphenol polyether oligomer composition comprises: a totalhalide content of less than 1000 ppm, less than 1000 ppm of —CH₂OHgroups, less than 5 wt. % cyclic oligomers, and less than 100 ppm of abisphenol of the formula

wherein R^(a), R^(b), X^(a), p and q are the same as in the oligomer. 2.The bisphenol polyether oligomer composition of claim 1, wherein thecomposition does not exhibit a half maximal inhibitory concentration(IC₅₀) less than 0.00025 M for alpha or beta in vitro estradiolreceptors.
 3. The bisphenol polyether oligomer composition of claim 1,wherein the oligomer is of the formula

wherein G is H or

and the bisphenol is bisphenol A.
 4. The bisphenol polyether oligomercomposition of claim 1, wherein the oligomer is a phthalimidine oligomerof the formula

wherein R^(a), R^(b), and R^(c) are each independently a C₁₋₁₂ alkyl,C₁₋₁₂ alkoxy, or C₁₋₁₂ alkylarylene, R³ is each independently a C₁₋₆alkyl, R⁴ is hydrogen, C₁₋₆ alkyl, or a substituted or unsubstitutedphenyl, p, q, j, and t are each independently integers of 0 to 4, and nis 1 to 10; and wherein the bisphenol is of the formula

wherein R^(a), R^(b), R³, R⁴, p, q, and j are the same as defined forthe phthalimidine oligomer.
 5. The bisphenol polyether oligomercomposition of claim 4, wherein R⁴ is methyl or phenyl, and p, q, j, andt are
 0. 6. The bisphenol polyether oligomer composition of claim 1,wherein the oligomer is a bisphenol A-phthalimidine polyether oligomerof the formula

wherein R^(a), R^(b), and R^(c) are each independently a C₁₋₁₂ alkyl,C₁₋₁₂ alkoxy, or C₁₋₁₂ alkylarylene, R³ is each independently a C₁₋₆alkyl, R⁴ is hydrogen, C₁₋₆ alkyl, or a substituted or unsubstitutedphenyl, p, q, j, and t are each independently integers of 0 to 4, α is 1to 10 and β is 1 to 10, provided that α+β is 2 to 10, G is H or

and A is

and wherein the bisphenol is bisphenol A, a bisphenol of the formula(3b)

wherein R^(a), R^(b), R³, R⁴, p, q, and j are the same as defined forthe bisphenol A-phthalimidine polyether oligomer, or a combination ofbisphenol A and a bisphenol of formula (3b).
 7. A polyetherpolycarbonate comprising repeating carbonate unit of the formula

wherein R^(a), R^(b), and R^(c) are each independently a C₁₋₁₈ alkyl,C₁₋₁₈ alkoxy or alkylarylene, each occurrence of X^(a) is independentlysingle bond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—, or a C₁₋₁₈ organicgroup, p, q, and t are each independently integers of 0 to 4; and n is 1to
 10. 8. The polyether polycarbonate of claim 7, comprising from 5 to500 of polycarbonate repeat units.
 9. The polyether polycarbonate ofclaim 7, wherein each thermolytic and hydrolytic degradation product ofeach of the repeating carbonate units in the polycarbonate does notexhibit a half maximal inhibitory concentration (IC₅₀) less than 0.00025M for alpha or beta in vitro estradiol receptors.
 10. The polyetherpolycarbonate of claim 7, wherein the polycarbonate has a glasstransition temperature of greater than 135° C.
 11. The polyetherpolycarbonate of claim 7, wherein the endcap is a phenoxy group.
 12. Thepolyether polycarbonate of claim 7, further having an Mw of 3,000 to80,000 Daltons, a phenolic end group content less than 20 meq/kg, atotal chloride content less than 50 ppm, a transition metal content lessthan 50 ppm, and a residual phenolic monomer content less than 100 ppm.13. The polyether polycarbonate of claim 7, wherein the repeatingcarbonate units are of the formula

wherein n is 1 to 10;

wherein n is 1 to 10;

wherein n is 1 to 10;

wherein R⁴ is phenyl or methyl and n is 1 to 10;

wherein a is 1 to 10 and β is 1 to 10, provided that α+β is 2 to 10, andA is

or a combination comprising at least one of the foregoing repeatingcarbonate units.
 14. The polyether polycarbonate of claim 7, wherein thepolycarbonate is a poly(ester carbonate) further comprising repeatingester units derived from a dicarboxylic acid monomer, and thedicarboxylic acid monomer does not exhibit a half maximal inhibitoryconcentration (IC₅₀) less than 0.00025 M for alpha or beta in vitroestradiol receptors.
 15. The polyether polycarbonate of claim 14,wherein the dicarboxylic acid monomer is a isophthalic acid,terephthalic acid, a C₆₋₃₆ aliphatic dicarboxylic acid, a hydroxybenzoic acid, or a combination comprising at least one of the foregoing.16. A polyether polycarbonate composition comprising the polyetherpolycarbonate of claim 7, and further comprising one or more additives,wherein each additive does not exhibit a half maximal inhibitoryconcentration (IC₅₀) less than 0.00025 M for alpha or beta in vitroestradiol receptors.
 17. The polyether polycarbonate of claim 16,wherein the additive is a stabilizer, antioxidant, colorant, impactmodifier, flame retardant, anti-drip additive, mold release additive,lubricant, plasticizer, mineral, reinforcement additive, or acombination comprising at least one of the foregoing.
 18. The polyetherpolycarbonate of claim 16, wherein the additive is a phosphoruscompound, wherein each hydrolysis product of the phosphorous compounddoes not exhibit a half maximal inhibitory concentration (IC₅₀) lessthan 0.00025 M for alpha or beta in vitro estradiol receptors.
 19. Thepolyether polycarbonate of claim 16, wherein the additive is aphosphite, wherein each hydrolysis product of the phosphite is does notexhibit a half maximal inhibitory concentration (IC₅₀) less than 0.00025M for alpha or beta in vitro estradiol receptors.
 20. The polyetherpolycarbonate composition of claim 16, further comprising a secondpolymer component comprising a non-polyether polycarbonate polymer. 21.The polymer composition of claim 20, wherein the second polymercomponent comprises a polycarbonate, polyester, polyolefin,polyetherimide, styrene-acrylonitrile, acrylonitrile-butadiene-styrene,methyl methacrylate, methyl methacrylate-butadiene-styrene,styrene-maleic anhydride, styrene-butadiene-styrene,styrene-ethylene-butylene-styrene, polystyrene, or a combinationcomprising at least one of the foregoing.
 22. An article comprising thepolyether polycarbonate composition of claim
 16. 23. A method ofmanufacture of an article comprises molding, extruding, or shaping thepolyether polycarbonate composition of claim 16 into an article.